Formation of SiOCN thin films

ABSTRACT

Methods for depositing silicon oxycarbonitride (SiOCN) thin films on a substrate in a reaction space are provided. The methods can include at least one plasma enhanced atomic layer deposition (PEALD) cycle including alternately and sequentially contacting the substrate with a silicon precursor and a second reactant that does not include oxygen. In some embodiments the methods allow for the deposition of SiOCN films having improved acid-based wet etch resistance.

REFERENCE TO RELATED APPLICATIONS

The present application is a continuation-in-part of U.S. patent application Ser. No. 14/939,984, filed on Nov. 12, 2015.

BACKGROUND

Field

The present disclosure relates generally to the field of semiconductor device manufacturing and, more particularly, to formation of silicon oxycarbonitride (SiOCN) films having desirable chemical resistance properties.

Description of the Related Art

There is increasing need for dielectric materials with relatively low dielectric constant (k) values and relatively low acid-based wet etch rates. Silicon oxycarbonitride may satisfy certain of these requirements. Typically, deposition processes for SiOCN require precursors comprising halides and/or oxygen plasma.

SUMMARY

In some embodiments plasma enhanced atomic layer deposition (PEALD) processes are provided for forming a silicon oxycarbonitride (SiOCN) thin film on a substrate in a reaction space. In some embodiments a PEALD process may comprise at least one deposition cycle comprising contacting a surface of the substrate with a vapor phase silicon precursor to thereby adsorb a silicon species on the surface of the substrate, contacting the adsorbed silicon species with at least one reactive species generated by plasma formed from a gas that does not comprise oxygen, and optionally repeating the contacting steps until a SiOCN film of a desired thickness has been formed. In some embodiments the silicon precursor use in a PEALD process has a formula as in one of the following general formulas: (R^(I)O)_(4-x)Si(R^(II)—NH₂)_(x)  (1)

wherein x is an integer from 1 to 4;

R^(I) is an independently selected alkyl group; and

R^(II) is an independently selected hydrocarbon; (R^(I)O)₃Si—R^(II)—NH₂  (2)

wherein R^(I) is an independently selected alkyl group; and

R^(II) is an independently selected hydrocarbon; and (R^(I)O)_(4-x)Si(—[CH₂]_(n)—NH₂)_(x)  (3)

wherein x is an integer from 1 to 4;

n is an integer from 1-5; and

R^(I) is an independently selected alkyl group.

In some embodiments a ratio of a wet etch rate of the SiOCN thin film to a wet etch rate of thermal silicon oxide may be less than about 5. In some embodiments a ratio of a wet etch rate of the SiOCN thin film to a wet etch rate of thermal silicon oxide may be less than about 0.3. In some embodiments a ratio of a wet etch rate of the SiOCN thin film to a wet etch rate of thermal silicon oxide may be less than about 0.1.

In some embodiments the SiOCN thin film may be deposited on a three-dimensional structure on the substrate. In some embodiments a wet etch rate ratio of a wet etch rate of SiOCN formed on a top surface of the three-dimensional structure to a wet etch rate of the SiOCN formed on a sidewall surface of the three-dimensional structure may be about 1:1, about 1:5, or less than about 2:1 in dilute HF.

In some embodiments the vapor phase silicon precursor may not comprise a halogen. In some embodiments the silicon precursor may comprise (3-aminopropyl)trimethoxysilane (APTMS). In some embodiments the reactive species may comprise hydrogen plasma, hydrogen atoms, hydrogen radicals, or hydrogen ions. In some embodiments the reactive species may be generated from a second reactant comprising a noble gas. In some embodiments the reactive species may further comprise nitrogen plasma, nitrogen atoms, nitrogen radicals, or nitrogen ions. In some embodiments the reactive species may be generated by plasma from a second reactant comprising hydrogen. In some embodiments the second reactant may comprise H₂.

In some embodiments the substrate surface may comprise an organic material. In some embodiments the organic material comprises a photoresist material.

In some embodiments the method may further comprise a hydrogen plasma treatment cycle carried out after a desired number of deposition cycles, the hydrogen plasma treatment cycle comprising contacting the substrate with a reactive species generated by a plasma from hydrogen. In some embodiments the hydrogen plasma treatment cycle may be carried out more than once during a deposition process. In some embodiments a ratio of hydrogen plasma treatment cycles deposition cycles is from about 1:1 to about 1:10. In some embodiments the at least one reactive species comprises reactive species generated by a plasma from N₂.

In some embodiments the method may further comprise a second hydrogen plasma deposition step performed after a desired number of deposition cycles have been carried out, the hydrogen plasma deposition step comprising at least one cycle comprising contacting a surface of the substrate with a vapor phase silicon precursor to form silicon species on the surface of the substrate; contacting the adsorbed silicon species with a reactive species generated by plasma formed from H₂; and optionally repeating the contacting steps until a SiOCN film of a desired thickness has been formed; wherein the silicon precursor has a formula as in one of the following general formulas: (R^(I)O)_(4-x)Si(R^(II)—NH₂)_(x)  (1)

wherein x is an integer from 1 to 4;

R^(I) is an independently selected alkyl group; and

R^(II) is an independently selected hydrocarbon; (R^(I)O)₃Si—R^(II)—NH₂  (2)

wherein R^(I) is an independently selected alkyl group; and

R^(II) is an independently selected hydrocarbon; (R^(I)O)_(4-x)Si(—[CH₂]_(n)—NH₂)_(x)  (3)

wherein x is an integer from 1 to 4;

n is an integer from 1-5; and

R^(I) is an independently selected alkyl group.

In some embodiments the method is used to form SiOCN spacers on a substrate in a spacer defined double patterning (SDDP) process. In some embodiments the method is used to form SiOCN spacers on a substrate in a spacer defined quadruple patterning (SQDP) process.

In some embodiments the SiOCN thin film may comprise at least 20 at % oxygen. In some embodiments the SiOCN thin film may comprise at least 5 at % carbon. In some embodiments the SiOCN thin film may comprise at least 5 at % nitrogen.

In some embodiments processes are provided for forming a silicon oxycarbonitride (SiOCN) thin film on a substrate in a reaction space. In some embodiments a process may comprise a plurality of deposition cycles, at least one deposition cycle may comprise alternately and sequentially contacting a surface of the substrate with a silicon precursor and a second reactant comprising at least one reactive species. In some embodiments a deposition cycle may be repeated two or more times to form the SiOCN thin film. In some embodiments the silicon precursor may have a general formula: L_(n)Si(OR^(I))_(4-x-y-z-n)(R^(II)NR^(III)R^(IV))_(x)H_(y)(OH)_(z)

wherein n is an integer from 0 to 3, x is an integer from 1 to 4, y is an integer from 0 to 3, z is an integer from 0 to 3; and 4-x-y-z-n is from 0 to 3;

R^(I) is an independently selected alkyl group;

R^(II) is an independently hydrocarbon;

R^(III) and R^(IV) are independently selected alkyl groups and/or hydrogen; and

L is an independently selected alkyl group or a halogen.

In some embodiments the at least one reactive species may be generated by plasma formed from a gas that does not comprise oxygen.

In some embodiments the silicon precursor may have a general formula: L_(n)Si(OR^(I))_(4-x-n)(R^(II)NR^(III)R^(IV))_(x)

wherein n is an integer from 0 to 3, x is an integer from 1 to 3;

L is an independently selected alkyl group or a halogen;

R^(I) is an independently selected alkyl group;

R^(II) is an independently selected hydrocarbon; and

R^(III) and R^(IV) are independently selected alkyl groups and/or hydrogen.

In some embodiments the silicon precursor may have a general formula: Si(OR^(I))_(4-x-y-z)(R^(II)NR^(III)R^(IV))_(x)H_(y)(OH)_(z)

wherein x is an integer from 1 to 4, y is an integer from 0 to 3, z is an integer from 0 to 3;

R^(I) is an independently selected alkyl group;

R^(II) is an independently selected hydrocarbon; and

R^(II) and R^(IV) are independently selected alkyl groups and/or hydrogen.

In some embodiments the silicon precursor may have a general formula: Si(OR)_(4-x)(R^(II)NR^(III)R^(IV))_(x)

wherein x is an integer from 1 to 4;

R^(I) is an independently selected alkyl group;

R^(II) is an independently selected hydrocarbon; and

R^(III) and R^(IV) are independently selected alkyl groups and/or hydrogen.

In some embodiments the silicon precursor may comprise APTMS. In some embodiments at least one deposition cycle may be a PEALD cycle. In some embodiments a reactive species may be generated by applying RF power of from about 100 Watts (W) to about 1000 W to the second reactant. In some embodiments a deposition cycle may be carried out at a process temperature of about 300° C. to about 400° C. In some embodiments the deposition cycle may be carried out at a process temperature of less than about 100° C. In some embodiments the substrate may comprise an organic material.

In some embodiments processes are provided for depositing a silicon oxycarbonitride (SiOCN) thin film on a substrate in a reaction space. In some embodiments such a process may comprise contacting a surface of the substrate with a silicon precursor comprising at least one ligand bonded through carbon to a silicon atom and containing an NH₂-group attached to a carbon chain and at least one ligand bonded to the silicon atom through an oxygen atom and in which an alkyl group is bonded to the oxygen atom. In some embodiments a process may further comprise exposing the substrate to a purge gas and/or vacuum to remove excess titanium reactant and reaction byproducts, if any, contacting a surface of the substrate with a second reactant comprising hydrogen, wherein the second reactant comprises at least one reactive species generated by plasma, exposing the substrate to a purge gas and/or vacuum to remove excess second reactant and reaction byproducts, if any, and repeating the contacting steps until a SiOCN thin film of desired thickness has been formed.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a process flow diagram for depositing a silicon oxycarbonitride (SiOCN) thin film by a plasma enhanced atomic layer deposition (PEALD) process according to some embodiments of the present disclosure.

FIG. 2 illustrates film growth per cycle (GPC), refractive index, and wet etch rate ratio (WERR) as a function of second reactant gas mixture ratio for SiOCN thin films deposited according to some embodiments of the present disclosure.

FIG. 3 illustrates etch amount (dHF wet etch) versus etch time for thermal oxide (TOX) and a SiOCN thin film deposited according to some embodiments of the present disclosure.

FIG. 4 is a compositional X-ray photoelectron spectroscopy (XPS) depth profile for a SiOCN thin film deposited according to some embodiments of the present disclosure.

FIGS. 5A-B illustrate transmission electron microscope (TEM) images of a SiOCN thin film deposited according to some embodiments of the present disclosure before and after exposure to a 2-minute dHF dip.

FIGS. 5C-D illustrate transmission electron microscope (TEM) images of a SiOCN thin film deposited according to some embodiments of the present disclosure before and after exposure to a 2-minute dHF dip.

FIG. 6 is a diagram generally illustrating a self aligned spacer formed with N plasma and O plasma.

FIG. 7 depicts a scanning electron micrograph of a sample SiOCN film deposited according to some embodiments before and after being exposed to 0.5 wt % dilute HF for 2 minutes.

DETAILED DESCRIPTION

Silicon oxycarbonitride (SiOCN) films have a wide variety of applications, as will be apparent to the skilled artisan, for example in integrated circuit fabrication. More specifically, SiOCN films that display a low etch rate have a wide variety of application, both in the semiconductor industry and outside of the semiconductor industry. SiOCN films may be useful as, for example, etch stop layers, sacrificial layers, low-k spacers, anti-reflection layers (ARL), and passivation layers.

According to some embodiments of the present disclosure, various SiOCN films, precursors, and methods for depositing said films are provided. In some embodiments the SiOCN films have a relatively low wet etch rate, for example in dHF.

In some embodiments SiOCN thin films are deposited on a substrate by plasma-enhanced atomic layer deposition (PEALD) processes. In some embodiments SiOCN thin films are not deposited by liquid phase methods. In some embodiments a SiOCN thin film is deposited over a three dimensional structure, such as a fin in the formation of a finFET device.

The formula of the silicon oxycarbonitride films is generally referred to herein as SiOCN for convenience and simplicity. As used herein, SiOCN is not intended to limit, restrict, or define the bonding or chemical state, for example the oxidation state of any of Si, O, C, N, and/or any other element in the film. Further, in some embodiments SiOCN thin films may comprise one or more elements in addition to Si, O, C, and/or N. In some embodiments the SiOCN films may comprise Si—C bonds, Si—O bonds, and/or Si—N bonds. In some embodiments the SiOCN films may comprise Si—C bonds and Si—O bonds and may not comprise Si—N bonds. In some embodiments the SiOCN films may comprise more Si—O bonds than Si—C bonds, for example a ratio of Si—O bonds to Si—C bonds may be from about 1:1 to about 10:1. In some embodiments the SiOCN films may comprise from about 0% to about 10% nitrogen on an atomic basis (at %). In some embodiments the SiOCN may comprise from about 0% to about 30% carbon on an atomic basis. In some embodiments the SiOCN films may comprise from about 0% to about 60% oxygen on an atomic basis. In some embodiments the SiOCN films may comprise about 0% to about 50% silicon on an atomic basis.

ALD-type processes are based on controlled, generally self-limiting surface reactions. Gas phase reactions are typically avoided by contacting the substrate alternately and sequentially with the reactants. Vapor phase reactants are separated from each other in the reaction chamber, for example, by removing excess reactants and/or reactant byproducts between reactant pulses. The reactants may be removed from proximity with the substrate surface with the aid of a purge gas and/or vacuum. In some embodiments excess reactants and/or reactant byproducts are removed from the reaction space by purging, for example with an inert gas.

In some embodiments, plasma enhanced ALD (PEALD) processes are used to deposit SiOCN films. In some embodiments PEALD processes as described herein do not comprise oxygen plasma. Briefly, a substrate or workpiece is placed in a reaction chamber and subjected to alternately repeated surface reactions. In some embodiments, thin SiOCN films are formed by repetition of a self-limiting ALD cycle. In some embodiments, for forming SiOCN films, each ALD cycle comprises at least two distinct phases. The contacting and removal of a reactant from the substrate may be considered a phase. In a first phase, a vapor phase first reactant comprising silicon contacts the substrate and forms no more than about one monolayer on the substrate surface. This reactant is also referred to herein as “the silicon precursor,” “silicon-containing precursor,” or “silicon reactant” and may be, for example, (3-Aminopropyl)trimethoxysilane (APTMS).

In a second phase, a second reactant comprising a reactive species contacts the substrate and may convert adsorbed silicon to SiOCN. In some embodiments the second reactant comprises a hydrogen precursor. In some embodiments, the reactive species comprises an excited species. In some embodiments the second reactant comprises a species from a hydrogen containing plasma. In some embodiments, the second reactant comprises hydrogen radicals, hydrogen atoms and/or hydrogen plasma. The second reactant may comprise other species that are not hydrogen precursors. In some embodiments, the second reactant may comprise a plasma of nitrogen, radicals of nitrogen, or atomic nitrogen in one form or another. In some embodiments, the second reactant may comprise a species from a noble gas, such as He, Ne, Ar, Kr, or Xe, for example as radicals, in plasma form, or in elemental form. These reactive species from noble gases do not necessarily contribute material to the deposited film, but can in some circumstances contribute to film growth as well as help in the formation and ignition of plasma. In some embodiments a gas that is used to form a plasma may flow constantly throughout the deposition process but only be activated intermittently. In some embodiments a gas that is used to form a plasma does not comprise oxygen. In some embodiments the adsorbed silicon precursor is not contacted with a reactive species generated by a plasma from oxygen. In some embodiments a second reactant comprising reactive species is generated in a gas that does not comprise oxygen. For example, in some embodiments a second reactant may comprise a plasma generated in a gas that does not comprise oxygen. In some embodiments the second reactant may be generated in a gas comprising less than about 1 atomic % (at %) oxygen, less than about 0.1 at % oxygen, less than about 0.01 at % oxygen, or less than about 0.001 at % oxygen.

In some embodiments the PEALD process may be varied, for example by first utilizing a second reactant comprising a plasma of nitrogen, radicals of nitrogen, or atomic nitrogen in one form or another for one or more deposition cycles to form a layer of a desired thickness and then utilizing a second reactant comprising hydrogen radicals, hydrogen atoms and/or hydrogen plasma once a SiOCN layer of a desired thickness has been deposited.

In some embodiments the PEALD process may utilize a second reactant comprising a reactive species generated by a plasma from an inert gas, for example a noble gas such as Ar or He for one or more deposition cycles to form a layer of a desired thickness and may then utilize a second reactant comprising hydrogen radicals, hydrogen atoms and/or hydrogen plasma once a SiOCN layer of a desired thickness has been deposited.

In some embodiments the PEALD processes described herein may be used to deposit a SiOCN thin film on a substrate comprising an organic surface, for example a surface comprising a photoresist material. In some embodiments a PEALD process as described herein may be used to deposit an SiOCN thin film on a substrate comprising a surface that is sensitive to degradation or deformation by hydrogen plasma, for example a photoresist surface. In some embodiments a process for depositing a SiOCN thin film may combine two different PEALD processes as described herein. For example, a first PEALD process utilizing a second reactant comprising a plasma of nitrogen, radicals of nitrogen, or atomic nitrogen in one form or another can deposit a SiOCN layer over an surface sensitive to hydrogen plasma that is thick enough to protect the surface from hydrogen plasma. Then a second PEALD process utilizing a second reactant comprising hydrogen radicals, hydrogen atoms and/or hydrogen plasma can deposit a further SiOCN layer of a desired thickness directly over the first SiOCN layer.

Additional phases may be added and phases may be removed as desired to adjust the composition of the final film.

One or more of the reactants may be provided with the aid of a carrier gas, such as Ar or He. In some embodiments the silicon precursor and the second reactant are provided with the aid of a carrier gas.

In some embodiments, two of the phases may overlap, or be combined. For example, the silicon precursor and the second reactant may be contact the substrate simultaneously in phases that partially or completely overlap. In addition, although referred to as the first and second phases, and the first and second reactants, the order of the phases may be varied, and an ALD cycle may begin with any one of the phases. That is, unless specified otherwise, the reactants can contact the substrate in any order, and the process may begin with any of the reactants.

As discussed in more detail below, in some embodiments for depositing a SiOCN film, one or more deposition cycles begin by contacting the substrate with the silicon precursor, followed by the second precursor. In other embodiments deposition may begin by contacting the substrate with the second precursor, followed by the silicon precursor.

In some embodiments the substrate on which deposition is desired, such as a semiconductor workpiece, is loaded into a reaction space or reactor. The reactor may be part of a cluster tool in which a variety of different processes in the formation of an integrated circuit are carried out. In some embodiments a flow-type reactor is utilized. In some embodiments a shower head type of reactor is utilized. In some embodiments, a space divided reactor is utilized. In some embodiments a high-volume manufacturing-capable single wafer ALD reactor is used. In other embodiments a batch reactor comprising multiple substrates is used. For embodiments in which batch ALD reactors are used, the number of substrates is in the range of 10 to 200, in the range of 50 to 150, or in the range of 100 to 130.

Examples of suitable reactors that may be used include commercially available equipment such as Pulsar® reactors—such as the Pulsar® 2000 and the Pulsar® 3000—EmerALD® reactor and Advance® 400 Series reactors, available from ASM America, Inc of Phoenix, Ariz. and ASM Europe B.V., Almere, Netherlands. Other commercially available reactors include those from ASM Japan K.K (Tokyo, Japan) under the tradename Eagle® XP and XP8.

In some embodiments, if necessary, the exposed surfaces of the workpiece can be pretreated to provide reactive sites to react with the first phase of the ALD process. In some embodiments a separate pretreatment step is not required. In some embodiments the substrate is pretreated to provide a desired surface termination. In some embodiments the substrate is pretreated with plasma.

In some embodiments a pretreatment step may comprise depositing an organic material on at least a portion of the surface of the substrate. However, in some embodiments a substrate that already comprises an organic material may be provided. In some embodiments a pretreatment step may comprise depositing a polymer material on at least a portion of the surface of the substrate. For example, in some embodiments a pretreatment step may comprise forming a polyimide, polyamide, polystyrene, polyurea, or other such polymer material on at least a portion of the substrate. In some embodiments the polymers may include dimers, trimers, polyurethanes, polythioureas, polyesters, or polyimines. In some embodiments the formed organic material may comprise other polymeric forms or mixtures of the above materials.

In some embodiments a pretreatment step may comprise depositing or forming a layer comprising a resist material, such as photoresist. That is, in some embodiments a pretreatment step may comprise forming or depositing a layer comprising a light sensitive material capable of being used in, for example, photolithography or photoengraving processes. For example, in some embodiments a pretreatment step may comprise forming or depositing a photoresist material capable of being used in an extreme ultraviolet lithography process, otherwise referred to as an EUV resist. In some embodiments a pretreatment step may comprise forming or depositing a photoresist capable of being used in an immersion lithography process, for example a photoresist capable of being used in an immersion lithography process using light at a wavelength of 193 nm, otherwise referred to as a 193i resist.

Excess reactant and reaction byproducts, if any, are removed from the vicinity of the substrate, and in particular from the substrate surface, between reactant contacting phases. In some embodiments excess reactant and reaction byproducts, if any, are removed from the substrate surface by, for example, purging the reaction chamber between reactant contacting phases, such as by purging with an inert gas. The flow rate and contacting time of each reactant is tunable, as is the removal step, allowing for control of the quality and various properties of the films.

As mentioned above, in some embodiments a gas is provided to the reaction chamber continuously during each deposition cycle, or during the entire ALD process, and reactive species are provided by generating a plasma in the gas, either in the reaction chamber or upstream of the reaction chamber. In some embodiments the gas comprises nitrogen. In some embodiments the gas is nitrogen. In some embodiments the gas may comprise noble gas, such as helium or argon. In some embodiments the gas is helium or nitrogen. The flowing gas may also serve as a purge gas for the first and/or second reactant (or reactive species). For example, flowing nitrogen may serve as a purge gas for a first silicon precursor and also serve as a second reactant (as a source of reactive species). In some embodiments, nitrogen, argon, or helium may serve as a purge gas for a first precursor and a source of excited species for converting the silicon precursor to the SiOCN film. In some embodiments the gas in which the plasma is generated does not comprise nitrogen and the adsorbed silicon precursor is not contacted with a reactive species generated by a plasma from nitrogen. In some embodiments the gas in which the plasma is generated does not comprise oxygen and the adsorbed silicon precursor is not contacted with a reactive species generated by a plasma from oxygen.

The cycle is repeated until a film of the desired thickness and composition is obtained. In some embodiments the deposition parameters, such as the precursor flow rate, contacting time, removal time, and/or reactants themselves, may be varied in one or more deposition cycles during the ALD process in order to obtain a film with the desired characteristics.

In some embodiments the surface of the substrate is contacted with a reactant. In some embodiments a pulse of reactant is provided to a reaction space containing the substrate. The term “pulse” may be understood to comprise feeding reactant into the reaction chamber for a predetermined amount of time. The term “pulse” does not restrict the length or duration of the pulse and a pulse can be any length of time. In some embodiments the substrate is moved to a reaction space containing a reactant. In some embodiments the substrate is subsequently moved from a reaction space containing a first reactant to a second, different reaction space containing the second reactant.

In some embodiments, the substrate is contacted with the silicon reactant first. After an initial surface termination, if necessary or desired, the substrate is contacted with a first silicon reactant. In some embodiments a first silicon reactant pulse is supplied to the workpiece. In accordance with some embodiments, the first reactant pulse comprises a carrier gas flow and a volatile silicon species, such as APTMS, that is reactive with the workpiece surfaces of interest. Accordingly, the silicon reactant adsorbs upon these workpiece surfaces. The first reactant pulse self-saturates the workpiece surfaces such that any excess constituents of the first reactant pulse do not further react with the molecular layer formed by this process.

The first silicon reactant pulse can be supplied in gaseous form. The silicon precursor gas is considered “volatile” for purposes of the present description if the species exhibits sufficient vapor pressure under the process conditions to transport the species to the workpiece in sufficient concentration to saturate exposed surfaces.

In some embodiments the silicon reactant contacts the surface from about 0.05 seconds to about 5.0 seconds, about 0.1 seconds to about 3 seconds or about 0.2 seconds to about 1.0 seconds. The optimum contacting time can be readily determined by the skilled artisan based on the particular circumstances.

After sufficient time for about a molecular layer to adsorb on the substrate surface, excess first silicon reactant, and reaction byproducts, if any, are removed from the substrate surface. In some embodiments removing excess reactant and reaction byproducts, if any, may comprise purging the reaction chamber. In some embodiments the reaction chamber may be purged by stopping the flow of the first reactant while continuing to flow a carrier gas or purge gas for a sufficient time to diffuse or purge excess reactants and reactant by-products, if any, from the reaction space. In some embodiments the excess first precursor is purged with the aid of inert gas, such as nitrogen or argon, which is flowing throughout the ALD cycle. In some embodiments the substrate may be moved from the reaction space containing the first reactant to a second, different reaction space. In some embodiments, the first reactant is removed for about 0.1 seconds to about 10 seconds, about 0.3 seconds to about 5 seconds or about 0.3 seconds to about 1 second. Contacting and removal of the silicon reactant can be considered the first or silicon phase of the ALD cycle.

In the second phase, a second reactant comprising a reactive species, such as hydrogen plasma is provided to the workpiece. Hydrogen plasma may be formed by generating a plasma in hydrogen in the reaction chamber or upstream of the reaction chamber, for example by flowing the hydrogen (H₂) through a remote plasma generator.

In some embodiments, plasma is generated in flowing H₂ gas. In some embodiments H₂ is provided to the reaction chamber before the plasma is ignited or hydrogen atoms or radicals are formed. In some embodiments the H₂ is provided to the reaction chamber continuously and hydrogen containing plasma, atoms or radicals is created or supplied when needed.

Typically, the second reactant, for example comprising hydrogen plasma, contacts the substrate for about 0.1 seconds to about 10 seconds. In some embodiments the second reactant, such as hydrogen containing plasma, contacts the substrate for about 0.1 seconds to about 10 seconds, 0.5 seconds to about 5 seconds or 0.5 seconds to about 2.0 seconds. However, depending on the reactor type, substrate type and its surface area, the second reactant contacting time may be even higher than about 10 seconds. In some embodiments, contacting times can be on the order of minutes. The optimum contacting time can be readily determined by the skilled artisan based on the particular circumstances.

In some embodiments the second reactant is provided in two or more distinct pulses, without introducing another reactant in between any of the two or more pulses. For example, in some embodiments a plasma, such as a hydrogen containing plasma, is provided in two or more sequential pulses, without introducing a Si-precursor in between the sequential pulses. In some embodiments during provision of plasma two or more sequential plasma pulses are generated by providing a plasma discharge for a first period of time, extinguishing the plasma discharge for a second period of time, for example from about 0.1 seconds to about 10 seconds, from about 0.5 seconds to about 5 seconds or about 1.0 seconds to about 4.0 seconds, and exciting it again for a third period of time before introduction of another precursor or a removal step, such as before the Si-precursor or a purge step. Additional pulses of plasma can be introduced in the same way. In some embodiments a plasma is ignited for an equivalent period of time in each of the pulses.

In some embodiments plasma, for example hydrogen containing plasma may be generated by applying RF power of from about 10 W to about 2000 W, from about 50 W to about 1000 W, or from about 100 W to about 500 W in some embodiments. In some embodiments, a plasma power used for generating a nitrogen-containing plasma can be about 500 W to about 1,500 W, 700 W to about 1200 W or about 800 W to about 1,000 W. In some embodiments the RF power density may be from about 0.02 W/cm² to about 2.0 W/cm², or from about 0.05 W/cm² to about 1.5 W/cm². The RF power may be applied to second reactant that flows during the plasma contacting time, that flows continuously through the reaction chamber, and/or that flows through a remote plasma generator. Thus in some embodiments the plasma is generated in situ, while in other embodiments the plasma is generated remotely. In some embodiments a showerhead reactor is utilized and plasma is generated between a susceptor (on top of which the substrate is located) and a showerhead plate. In some embodiments the gap between the susceptor and showerhead plate is from about 0.1 cm to about 20 cm, from about 0.5 cm to about 5 cm, or from about 0.8 cm to about 3.0 cm.

After a time period sufficient to completely saturate and react the previously adsorbed molecular layer with the plasma pulse, any excess reactant and reaction byproducts are removed from the substrate surface.

In some embodiments removing excess reactant and reaction byproducts, if any, may comprise purging the reaction chamber. In some embodiments the reaction chamber may be purged by stopping the flow of the second reactant while continuing to flow a carrier gas or purge gas for a sufficient time to diffuse or purge excess reactants and reactant by-products, if any, from the reaction space. In some embodiments the excess second precursor is purged with the aid of inert gas, such as nitrogen or argon, which is flowing throughout the ALD cycle. In some embodiments the substrate may be moved from the reaction space containing the second reactant to a different reaction space. The removal may, in some embodiments, be from about 0.1 seconds to about 10 seconds, about 0.1 seconds to about 4 seconds or about 0.1 seconds to about 0.5 seconds. Together, the reactive species contacting and removal represent a second, reactive species phase in a SiOCN atomic layer deposition cycle.

The two phases together represent one ALD cycle, which is repeated to form SiOCN thin films of a desired thickness. While the ALD cycle is generally referred to herein as beginning with the silicon phase, it is contemplated that in other embodiments the cycle may begin with the reactive species phase. One of skill in the art will recognize that the first precursor phase generally reacts with the termination left by the last phase in the previous cycle. Thus, while no reactant may be previously adsorbed on the substrate surface or present in the reaction space if the reactive species phase is the first phase in the first ALD cycle, in subsequent cycles the reactive species phase will effectively follow the silicon phase. In some embodiments one or more different ALD cycles are provided in the deposition process.

According to some embodiments of the present disclosure, PEALD reactions may be performed at temperatures ranging from about 25° C. to about 700° C., from about 50° C. to about 600° C., from about 100° C. to about 450° C., or from about 200° C. to about 400° C. In some embodiments, the optimum reactor temperature may be limited by the maximum allowed thermal budget. Therefore, in some embodiments the reaction temperature is from about 300° C. to about 400° C. In some applications, the maximum temperature is around about 400° C., and, therefore the PEALD process is run at that reaction temperature.

The substrate on which a thin film is deposited may comprise various types of materials. In some embodiments the substrate may comprise an integrated circuit workpiece. In some embodiments the substrate may comprise silicon. In some embodiments the substrate may comprise silicon oxide, for example, thermal oxide. In some embodiments the substrate may comprise a high-k dielectric material. In some embodiments the substrate may comprise carbon. For example the substrate may comprise an amorphous carbon layer, graphene, and/or carbon nanotubes.

In some embodiments the substrate may comprise a metal, including, but not limited to W, Cu, Ni, Co, and/or Al. In some embodiments the substrate may comprise a metal nitride, including, but not limited to TiN and/or TaN. In some embodiments the substrate may comprise a metal carbide, including, but not limited to TiC and/or TaC. In some embodiments the substrate may comprise a metal chalcogenide, including, but not limited to MoS₂, Sb₂Te₃, and/or GeTe. In some embodiments the substrate may comprise a material that would be oxidized by exposure to an oxygen plasma process, but not by a PEALD process as described herein.

In some embodiments a substrate used in the PEALD processes described herein may comprise an organic material. For example, the substrate may comprise an organic material such as a plastic, polymer, and/or photoresist. In some embodiments the substrate may comprise a polyimide, polyamide, polystyrene, polyurea, or other such polymer material.

In some embodiments a substrate may comprise a resist material, such as photoresist. That is, in some embodiments a substrate may comprise a light sensitive material capable of being used in, for example, photolithography or photoengraving processes. For example, in some embodiments a substrate may comprise a photoresist material capable of being used in an extreme ultraviolet lithography process, otherwise referred to as an EUV resist. In some embodiments a substrate may comprise a photoresist capable of being used in an immersion lithography process, for example a photoresist capable of being used in an immersion lithography process using light at a wavelength of 193 nm, otherwise referred to as a 193i resist.

In some embodiments where the substrate comprises an organic material the reaction temperature of a PEALD process may be less than the temperature at which the organic material may degrade or breakdown. In some embodiments where the substrate comprises an organic material the reaction temperature of a PEALD process may be less than about 200° C. In some embodiments the reaction temperature may be less than about 150° C., less than about 100° C., less than about 75° C., or less than about 50° C.

In some embodiments where a substrate comprises an organic material the maximum process temperature may be as low as 100° C. In some embodiments where the substrate comprises an organic material, the absence of a plasma generated from oxygen may allow for deposition of a SiOCN thin film on an organic material that may otherwise degrade in a deposition process including plasma generated from oxygen. In some embodiments a PEALD process as described herein including a second reactant comprising a plasma of nitrogen, radicals of nitrogen, or atomic nitrogen in one form or another may allow for deposition of a SiOCN thin film on an organic material that may otherwise degrade in a deposition process including plasma generated from oxygen or hydrogen. In some embodiments such a SiOCN thin film may serve as a protective layer for the organic material and may allow for deposition of a further SiOCN film by a PEALD process that may otherwise degrade or damage the organic material.

According to some embodiments of the present disclosure, the pressure of the reaction chamber during processing is maintained at from about 0.01 Torr to about 50 Torr, or from about 0.1 Torr to about 10 Torr. In some embodiments the pressure of the reaction chamber is greater than about 6 Torr, or about 20 Torr. In some embodiments, a SiOCN deposition process can be performed at a pressure of about 20 Torr to about 500 Torr, about 20 Torr to about 50 Torr, or about 20 Torr to about 30 Torr.

In some embodiments a SiOCN deposition process can comprise a plurality of deposition cycles, wherein at least one deposition cycle is performed in an elevated pressure regime. For example, a deposition cycle of a PEALD process may comprise alternately and sequentially contacting the substrate with a silicon precursor and a second reactant under the elevated pressure. In some embodiments, one or more deposition cycles of the PEALD process can be performed at a process pressure of about 6 Torr to about 500 Torr, about 6 Torr to about 50 Torr, or about 6 Torr to about 100 Torr. In some embodiments, the one or more deposition cycles can be performed at a process pressure of greater than about 20 Torr, including about 20 Torr to about 500 Torr, about 30 Torr to about 500 Torr, about 40 Torr to about 500 Torr, or about 50 Torr to about 500 Torr. In some embodiments, the one or more deposition cycles can be performed at a process pressure of about 20 Torr to about 30 Torr, about 20 Torr to about 100 Torr, about 30 Torr to about 100 Torr, about 40 Torr to about 100 Torr or about 50 Torr to about 100 Torr.

PEALD of SiOCN

As mentioned above, and discussed in more detail below, in some embodiments SiOCN thin films can be deposited on a substrate in a reaction space by a plasma enhanced atomic deposition layer (PEALD) process. According to some embodiments, a SiOCN thin film is deposited using a PEALD process on a substrate having three-dimensional features, such as in a FinFET application. In some embodiments a PEALD process as described herein may be used in a variety of applications. For example, a PEALD process as described herein may be used in the formation of hardmask layers, sacrificial layers, protective layers, or low-k spacers. A PEALD process as described herein may be used in, for example, memory device applications.

In some embodiments a SiOCN thin film may be deposited by a PEALD process as described herein on a substrate that is not able to withstand O plasma without damage, for example a substrate comprising an organic and/or photoresist material.

Referring to FIG. 1 and according to some embodiments a SiOCN thin film is deposited on a substrate in a reaction space by a PEALD deposition process 100 comprising at least one cycle comprising:

contacting the substrate with a vapor phase silicon-containing precursor at step 120 such that silicon species adsorb onto the surface of the substrate;

removing excess silicon-containing precursor and reaction byproducts, if any, from the substrate surface at step 130;

contacting the substrate with a second reactant comprising reactive species generated by plasma at step 140, thereby converting the adsorbed silicon species into SiOCN;

removing excess second reactant and reaction byproducts, if any, from the substrate surface at step 150; and

optionally repeating the contacting and removing steps at step 160 to form a SiOCN thin film of a desired thickness and composition.

In some embodiments step 140 may comprise remotely generating or forming plasma or reactive species before contacting the substrate with the second reactant.

According to some embodiments a SiOCN plasma enhanced ALD deposition cycle can be used to deposit a SiOCN thin film. In certain embodiments, a SiOCN thin film is formed on a substrate by an ALD-type process comprising multiple SiOCN deposition cycles, each SiOCN deposition cycle comprising:

contacting a substrate with a vapor phase silicon reactant such that a silicon compound adsorbs on the substrate surface;

exposing the substrate to a purge gas and/or vacuum;

contacting the substrate with reactive species generated by forming a plasma in a second reactant; and

exposing the substrate to a purge gas and/or vacuum;

optionally repeating the contacting and exposing steps until a SiOCN thin film of a desired thickness and composition is obtained.

In some embodiments the exposing the substrate to a purge gas and/or vacuum steps may comprise continuing the flow of an inert carrier gas while stopping the flow of a precursor or reactant. In some embodiments the exposing the substrate to a purge gas and/or vacuum steps may comprise stopping the flow of a precursor and a carrier gas into a reaction chamber and evacuating the reaction chamber, for example with a vacuum pump. In some embodiments the exposing the substrate to a purge gas and/or vacuum steps may comprise moving the substrate from a first reaction chamber to a second, different reaction chamber containing a purge gas. In some embodiments the exposing the substrate to a purge gas and/or vacuum steps may comprise moving the substrate from a first reaction chamber to a second, different reaction chamber under a vacuum.

According to some embodiments a SiOCN thin film is deposited on a substrate in a reaction space by a PEALD deposition process comprising at least one cycle comprising:

contacting the substrate with APTMS such that silicon species adsorb onto the surface of the substrate;

removing excess APTMS and reaction byproducts, if any, from the substrate surface;

contacting the substrate with a second reactant comprising reactive species generated by plasma, wherein the reactive species comprises hydrogen;

removing excess second reactant and reaction byproducts, if any, from the substrate surface; and

optionally repeating the contacting and removing steps to form a SiOCN thin film of a desired thickness and composition.

In some embodiments contacting the substrate with a second reactant may comprise remotely generating or forming plasma or reactive species before contacting the substrate with the second reactant.

In certain embodiments, a SiOCN thin film is formed on a substrate by an ALD-type process comprising multiple SiOCN deposition cycles, each SiOCN deposition cycle comprising: alternately and sequentially contacting the substrate with a first vapor phase silicon precursor and a second reactant comprising reactive species. In some embodiments the silicon precursor may comprise APTMS and the second reactive species may comprise hydrogen.

For example, as discussed above, in some embodiments SiOCN may be deposited on a surface that may be degraded by a PEALD processes as described herein including hydrogen plasma as a second reactant, for example organic surfaces. Thus, in some embodiments a PEALD process for depositing a SiOCN film may start with a number of deposition cycles utilizing a plasma generated from a nitrogen-containing gas and/or an inert gas such as a noble gas as a second reactant in order to form a first SiOCN layer that can act as a passivation layer or protective layer for the organic surface. Further SiOCN material may then be deposited on the first SiOCN layer utilizing deposition cycles including a second reactant comprising hydrogen plasma.

In some embodiments a SiOCN thin film may be deposited on a substrate in a reaction space by a method including:

a first plasma deposition process comprising two or more deposition cycles that comprise:

-   -   contacting the substrate with a vapor phase silicon-containing         precursor such that silicon species adsorb onto the surface of         the substrate;     -   removing excess silicon-containing precursor and reaction         byproducts, if any, from the substrate surface;     -   contacting the substrate with a second reactant comprising         reactive species generated by plasma from an inert gas such as a         nitrogen-containing gas and/or a noble gas or gases;     -   removing excess second reactant and reaction byproducts, if any,         from the substrate surface; and     -   optionally repeating the contacting and removing steps to form a         first SiOCN layer of a desired thickness and composition;

and a second hydrogen-containing plasma deposition process comprising two or more deposition cycles that comprise:

-   -   contacting the substrate with a vapor phase silicon-containing         precursor such that silicon species adsorb onto the surface of         the substrate;     -   removing excess silicon-containing precursor and reaction         byproducts, if any, from the substrate surface;     -   contacting the substrate with a second reactant comprising         reactive species generated by plasma, wherein the reactive         species comprises hydrogen;     -   removing excess second reactant and reaction byproducts, if any,         from the substrate surface; and     -   optionally repeating the contacting and removing steps to form a         second SiOCN layer of a desired thickness and composition.

In some embodiments the first SiOCN layer and the second SiOCN layer may not be separate layers and may form a continuous SiOCN film of a desired thickness. In some embodiments the first SiOCN layer may by a distinct layer from the second SiOCN layer. In some embodiments the second SiOCN layer may have a lower density than the first SiOCN layer. In some embodiments a SiOCN film deposited by a method including a first plasma deposition process and a second hydrogen-containing plasma deposition process may have a lower density as compared to a SiOCN film deposited by a method that does not include H₂ plasma.

In some embodiments the first plasma deposition process does not include hydrogen plasma and may include any number of deposition cycles. However, in some embodiments the first plasma deposition process may have enough deposition cycles to form a SiOCN layer thick enough to protect the underlying material from degradation due to the second hydrogen-containing plasma deposition process. For example, in some embodiments the thickness of the first SiOCN layer deposited by the first plasma deposition process may be up to about 20 nm thick. In some embodiments the first SiOCN layer may have a thickness greater than or equal to about 0.1 nm to about 3 nm. In some embodiments the first SiOCN layer may have a thickness greater than or equal to about 3 nm, greater than or equal to about 4 nm, or greater than or equal to about 5 nm.

In some embodiments the first plasma deposition process may include greater than or equal to about 5 deposition cycles, greater than or equal to about 10 deposition cycles, greater than or equal to about deposition 20 cycles, greater than or equal to about deposition 50 cycles, greater than or equal to about 100 deposition cycles, or greater than or equal to about 250 deposition cycles. In some embodiments the first plasma deposition process may include less than or equal to about 500 deposition cycles, less than or equal to about 250 deposition cycles, less than or equal to about 100 deposition cycles, less than or equal to about 50 deposition cycles, less than or equal to about 30 deposition cycles, or less than or equal to about 20 deposition cycles.

In some embodiments the hydrogen-containing deposition process may include any number of deposition cycles. In some embodiments the number of deposition cycles in the nitrogen-containing plasma deposition process and the number of deposition cycles in the hydrogen-containing plasma deposition process may be independently selected.

In some embodiments the substrate may comprise an organic surface. In some embodiments the substrate may comprise a polymer surface. For example, in some embodiments the substrate may comprise a polyimide, polyamide, polystyrene, polyuria, or other such polymer. In some embodiments the polymers may include dimers, trimers, polyurethanes, polythioureas, polyesters, or polyimines. In some embodiments the organic surface may comprise other polymeric forms or mixtures of the above materials. In some embodiments the organic material may comprise graphene or another form of carbon. In some embodiments the organic material may comprise amorphous carbon. In some embodiments the amorphous carbon may contain hydrogen. In some embodiments the substrate may comprise a photoresist material. In some embodiments there is no hydrocarbon contamination of the substrate surface, for example from the atmosphere.

In some embodiments, the substrate surface may comprise a resist, such as photoresist. That is, in some embodiments the substrate surface may comprise a light sensitive material capable of being used in, for example, photolithography or photoengraving processes. For example, in some embodiments the substrate surface may comprise a photoresist capable of being used in an extreme ultraviolet lithography process, otherwise referred to as an EUV resist. In some embodiments the substrate surface may comprise a photoresist capable of being used in an immersion lithography process, for example a photoresist capable of being used in an immersion lithography process using light at a wavelength of 193 nm, otherwise referred to as a 193i resist.

In some embodiments where the substrate may comprise an organic material, the first SiOCN layer formed by the first plasma deposition process may act as a protective layer for the organic material. That is, in some embodiments the first SiOCN layer may serve to protect the organic material from degradation or removal during subsequent processes, for example during the second hydrogen-containing plasma deposition process. In some embodiments the first SiOCN layer may serve to prevent hydrogen plasma from contacting, degrading, or removing the organic material during the second hydrogen-containing plasma deposition process.

In some embodiments where the substrate comprises an organic surface a SiOCN deposition method including a first plasma deposition process and a hydrogen-containing plasma deposition process may remove or degrade less than about 40%, less than about 30%, less than about 20%, less than about 10%, less than about 5%, or less than about 1% of the organic surface as measured by the thickness of the organic surface. In some embodiments a method of depositing SiOCN may not remove or degrade substantially any material from the organic surface.

In some embodiments, methods of forming a SiOCN thin film on a substrate in a reaction space can include a plurality of deposition cycles comprising alternately and sequentially contacting the substrate with a vapor phase silicon-containing precursor and a second reactant comprising reactive species generated by plasma from a nitrogen-containing gas and/or an inert gas such as a noble gas. In some embodiments the method can further comprise a hydrogen plasma treatment cycle comprising contacting the substrate with a second reactant comprising reactive species generated by plasma, wherein the reactive species comprises hydrogen, wherein the hydrogen plasma treatment cycle can be optionally performed after a desired number of deposition cycles. In some embodiments further deposition cycles may be performed after a hydrogen plasma treatment cycle.

In some embodiments a hydrogen plasma treatment cycle may be performed in every n deposition cycles, where n is an integer. In some embodiments a hydrogen plasma treatment cycle may be performed in every 1, 5, 10, 25, 50, 100, 500, 2000, or more deposition cycles. For example, in some embodiments one hydrogen plasma treatment cycle may be performed for every 5 deposition cycles in a SiOCN deposition method including 50 deposition cycles. In some embodiments the deposition cycles may include a second reactant comprising reactive species generated by a plasma from N₂.

In some embodiments a first hydrogen plasma treatment cycle may be performed in a first number of deposition cycles, such as nitrogen-containing plasma deposition cycles, and a second hydrogen plasma treatment cycle may be performed in a second, different number of deposition cycles. That is, in some embodiments a ratio of hydrogen plasma treatment cycles to deposition cycles may be from 1:1 to 1:2000, from 1:1 to 1:500, from 1:1 to 1:100, from 1:1 to 1:50, from 1:1 to 1:25, from 1:1 to 1:10, from 1:1 to 1:5, or from 1:1 to 1:2.

In some embodiments a hydrogen plasma treatment cycle may comprise contacting the substrate with a reactive species comprising hydrogen for about 0.1 seconds to about 20 seconds. In some embodiments the reactive species comprising hydrogen contacts the substrate for about 0.1 seconds to about 10 seconds, 0.5 seconds to about 5 seconds or 0.5 seconds to about 2.0 seconds. In some embodiments a hydrogen plasma treatment cycle may comprise contacting the substrate with a reactive species comprising hydrogen for about 4 seconds. However, depending on the reactor type, substrate type and its surface area, desired film characteristics, and other factors, the reactive species comprising hydrogen contacting time may be even higher than about 20 seconds. In some embodiments, contacting times can be on the order of minutes. The optimum contacting time can be readily determined by the skilled artisan based on the particular circumstances.

In some embodiments the silicon-containing precursor can comprise APTMS. In some embodiments the second reactant of a deposition cycle may comprise reactive species generated by a plasma from N₂. In some embodiments the second reactant of a hydrogen plasma treatment cycle may comprise species generated by a plasma from H₂.

In some embodiments, the PEALD process is performed at a temperature between about 100° C. to about 650° C., about 100° C. to about 550° C., about 100° C. to about 450° C., about 200° C. to about 600° C., or at about 200° C. to about 400° C. In some embodiments the temperature is about 300° C. In some embodiments, for example where a substrate comprises an organic material such as an organic photoresist, the PEALD process may be performed at a temperature less than about 100° C. In some embodiments the PEALD process is performed at a temperature less than about 75° C., or less than about 50° C. In some embodiments a plasma may be generated by applying RF power to the second reactant. The RF power may be applied to second reactant to thereby generate reactive species. In some embodiments the RF power may be applied to the second reactant that flows continuously through the reaction chamber, and/or that flows through a remote plasma generator. Thus in some embodiments the plasma is generated in situ, while in other embodiments the plasma is generated remotely. In some embodiments the RF power applied to the second reactant is from about 10 W to about 2000 W, from about 100 W to about 1000 W or from about 200 W to about 500 W. In some embodiments the RF power applied to the second reactant is about 200 W. In some embodiments, a plasma power used for generating a nitrogen-containing plasma can be about 500 W to about 1500 W, about 800 W to about 1200 W.

As discussed in more detail below, in some embodiments for depositing a SiOCN film, one or more PEALD deposition cycles begin with provision of the silicon precursor, followed by the second reactant. In other embodiments deposition may begin with provision of the second reactant, followed by the silicon precursor. One of skill in the art will recognize that the first precursor phase generally reacts with the termination left by the last phase in the previous cycle. Thus, while no reactant may be previously adsorbed on the substrate surface or present in the reaction space if the reactive species phase is the first phase in the first PEALD cycle, in subsequent PEALD cycles the reactive species phase will effectively follow the silicon phase. In some embodiments one or more different PEALD sub-cycles are provided in the process for forming a SiOCN thin film.

Si Precursors

A number of different suitable Si precursors can be used in the presently disclosed PEALD processes. In some embodiments, at least some Si precursors suitable for deposition of SiOCN by PEALD processes have the following general formula: Si(OR^(I))_(4-x)(R^(II)NR^(III)R^(IV))_(x)  (1)

Wherein x=1-4, R^(I) may be an independently selected alkyl group, R^(II) may be an independently selected hydrocarbon group, and R^(III) and RV may be independently selected alkyl groups and/or hydrogens. In some embodiments R^(I) and R^(II) are C₁-C₃ alkyl ligands, such as methyl, ethyl, n-propyl, or isopropyl. In some embodiments R^(I) may be a C₁-C₄ alkyl ligand, such as methyl, ethyl, n-propyl, isopropyl, or tertbutyl. In some embodiments R^(II) is not a C₃ hydrocarbon. In some embodiments R^(II) is a C₁-C₂ hydrocarbon or a C₄-C₆ hydrocarbon. In some embodiments R^(II) may be an unsaturated hydrocarbon, such as a hydrocarbon containing one or more double bonds. In some embodiments R^(II) may be an alkyl group where one of the hydrogens is removed. In some embodiments R^(III) and R^(IV) are hydrogen. In some embodiments R^(I) is methyl, R^(II) is n-propyl, R^(III) is hydrogen, R^(IV) is hydrogen, and x=1.

For example, an Si precursor may have the formula (written in a more detailed manner in order to show bonding): (R^(I)—O—)_(4-x)Si(—R^(II)—NR^(III)R^(IV))_(x), wherein x=1-4, R^(I) may be an independently selected alkyl group, R^(II) may be an independently selected hydrocarbon, and R^(III) and R^(IV) may be independently selected alkyl groups and/or hydrogens.

According to some embodiments, some Si precursors may have the following general formula: Si(OR^(I))_(4-x-y-z)(R^(II)NR^(III)R^(IV))_(x)H_(y)(OH)_(z)  (2)

wherein x=1-4, y=0-3, and z=0-3, R^(I) and R^(II) may be an independently selected alkyl group, R^(II) may be an independently selected hydrocarbon, and R^(III) and R^(IV) may be independently selected alkyl groups and/or hydrogens. In some embodiments R^(II) may be an unsaturated hydrocarbon, such as a hydrocarbon containing one or more double bonds. In some embodiments R^(II) may be an alkyl group where one of the hydrogens is removed.

According to some embodiments, some Si precursors may have the following general formula: L_(n)Si(OR^(I))_(4-x-n)(R^(II)NR^(III)R^(IV))_(x)  (3)

wherein n=1-3, x=0-3, R^(I) may be an independently selected alkyl group, R^(II) may be an independently selected hydrocarbon, and R^(III) and R^(IV) may be independently selected alkyl groups and/or hydrogens, and L is an independently selected alkyl group or halogen. In some embodiments R^(II) may be an unsaturated hydrocarbon, such as a hydrocarbon containing one or more double bonds. In some embodiments R^(II) may be an alkyl group where one of the hydrogens is removed.

According to some embodiments, some Si precursors may have the following general formula: L_(n)Si(OR^(I))_(4-x-y-z-n)(R^(II)NR^(III)R^(IV))_(x)H_(y)(OH)_(z)  (4)

wherein n=0-3 x=1-4, y=0-3, z=0-3, R^(I) may be an independently selected alkyl group, R^(II) may be an independently selected hydrocarbon, and R^(III) and R^(IV) may be independently selected alkyl groups and/or hydrogens, and L is an independently selected alkyl group or halogen. In some embodiments R^(II) may be an unsaturated hydrocarbon, such as a hydrocarbon containing one or more double bonds. In some embodiments R^(II) may be an alkyl group where one of the hydrogens is removed.

According to some embodiments, some Si precursors may have the following general formula: (R^(I)O)_(4-x)Si(R^(II)—NH₂)_(x)  5)

wherein x=1-4, R^(I) may be an independently selected alkyl group, and R^(I) may be an independently selected hydrocarbon. In some embodiments R^(I) and R^(II) are C₁-C₃ alkyl ligands, such as methyl, ethyl, n-propyl, or isopropyl. In some embodiments R^(I) is methyl, R^(II) is n-propyl and x=1. In some embodiments R^(II) may be an unsaturated hydrocarbon, such as a hydrocarbon containing one or more double bonds. In some embodiments R^(II) may be an alkyl group where one of the hydrogens is removed.

According to some embodiments, some Si precursors may have the following general formula: (R^(I)O)₃Si—R^(II)—NH₂  6)

Wherein, R^(I) may be an independently selected alkyl group, and R^(II) may be an independently selected hydrocarbon. In some embodiments R^(I) and R^(II) are C₁-C₃ alkyl ligands, such as methyl, ethyl, n-propyl, or isopropyl. In some embodiments R^(II) may be an unsaturated hydrocarbon, such as a hydrocarbon containing one or more double bonds. In some embodiments R^(II) may be an alkyl group where one of the hydrogens is removed.

According to some embodiments, some Si precursors may have the following general formula: (R^(I)O)_(4-x)Si(—[CH₂]_(n)—NH₂)_(x)  7)

wherein x=1-4, n=1-5, and R^(I) may be an independently selected alkyl group. In some embodiments R^(I) is a C₁-C₄ alkyl ligand, such as methyl, ethyl, n-propyl, or isopropyl. In some embodiments R^(I) is methyl, and x=1.

In some embodiments the silicon precursor does not comprise a halogen. In some embodiments the silicon precursor may comprise at least one aminoalkyl ligand. According to some embodiments a suitable silicon precursor may comprise at least one ligand which is bonded through carbon to silicon and contains at least one NH₂-group attached to a carbon chain, for example an aminoalkyl ligand. According to some embodiments a suitable silicon precursor may comprise at least one ligand which is bonded through carbon to silicon and contains an NH₂-group attached to a carbon chain, for example an aminoalkyl ligand, and may also comprise at least one ligand which is bonded to silicon through an oxygen atom and in which an alkyl group is bonded to oxygen, for example an alkoxide ligand. According to some embodiments a suitable silicon precursor may comprise at least one ligand which is bonded through carbon to silicon and contains at least one NR^(III)R^(IV)-group, wherein R^(III) and R^(IV) may be independently selected alkyl groups and/or hydrogens, attached to a carbon chain, for example an aminoalkyl ligand. According to some embodiments a suitable silicon precursor may comprise at least one ligand which is bonded through carbon to silicon and in which ligand at least one nitrogen is bonded to carbon. Further the one ligand which is bonded through carbon to silicon and in which ligand at least one nitrogen is bonded to carbon may comprise hydrogen bonded to nitrogen. According to some embodiments, in addition to a ligand which is bonded to silicon through carbon, a suitable silicon precursor may comprise also an alkoxy ligand, such as methoxy, ethoxy, n-propoxy, i-propoxy or tertbutoxy ligand. According to some embodiments, including some of the formulas of the above, a suitable silicon precursor comprises a carbon chain which is bonded to silicon through carbon, and in which there is an amino group, such as alkylamino or —NH₂ group, attached to the carbon chain and the carbon chain is a C1-C6 hydrocarbon, C2-C6 hydrocarbon or C2-C4 hydrocarbon, linear, branched or cyclic, containing only carbon and hydrogen. In some embodiments the carbon chain may be unsaturated and contain double carbon-carbon bonds. In some other embodiments the carbon chain may contain other atoms than carbon and hydrogen.

According to some embodiments suitable silicon precursors can include at least compounds having any of the general formulas (1) through (7). In some embodiments halides/halogens can include F, Cl, Br, and I. In some embodiments the silicon precursor can comprise (3-aminopropyl)trimethoxysilane (APTMS).

In some embodiments more than one silicon precursor may contact the substrate surface at the same time during an ALD phase. In some embodiments the silicon precursor may comprise more than one of the silicon precursors described herein. In some embodiments a first silicon precursor is used in a first ALD cycle and a second, different ALD precursor is used in a later ALD cycle. In some embodiments multiple silicon precursors may be used during a single ALD phase, for example in order to optimize certain properties of the deposited SiOCN film. In some embodiments only one silicon precursor may contact the substrate during the deposition. In some embodiments there may only be one silicon precursor and one second reactant or composition of second reactants in the deposition process. In some embodiments there is no metal precursor in the deposition process. In some embodiments the silicon precursor is not used as a silylating agent. In some embodiments the deposition temperature and/or the duration of the silicon precursor contacting step are selected such that the silicon precursor does not decompose. In some embodiments the silicon precursor may decompose during the silicon precursor contacting step. In some embodiments the silicon precursor does not comprise a halogen, such as chlorine or fluorine.

Second Reactants

As discussed above, the second reactant for depositing SiOCN according to the present disclosure may comprise a hydrogen precursor, which may comprise a reactive species. In some embodiments a reactive species includes, but is not limited to, radicals, plasmas, and/or excited atoms or species. Such reactive species may be generated by, for example, plasma discharge, hot-wire, or other suitable methods. In some embodiments the reactive species may be generated remotely from the reaction chamber, for example upstream from the reaction chamber (“remote plasma”). In some embodiments the reactive species may be generated in the reaction chamber, in the direct vicinity of the substrate, or directly above the substrate (“direct plasma”).

Suitable plasma compositions of a PEALD process include hydrogen reactive species, that is plasma, radicals of hydrogen, or atomic hydrogen in one form or another. In some embodiments a second reactant may comprise a reactive species formed at least in part from H₂. In some embodiments, nitrogen reactive species in the form of plasma, radicals of nitrogen, or atomic nitrogen in one form or another are also provided. And in some embodiments, a plasma may also contain noble gases, such as He, Ne, Ar, Kr and Xe, or Ar or He, in plasma form, as radicals, or in atomic form. In some embodiments, the second reactant does not comprise any species generated from oxygen. Thus, in some embodiments reactive species are not generated from a gas containing oxygen. In some embodiments a second reactant comprising reactive species is generated from a gas that does not contain oxygen. For example in some embodiments a second reactant may comprise a plasma generated from a gas that does not contain oxygen. In some embodiments the second reactant may be generated from a gas containing less than about 1 atomic % (at %) oxygen, less than about 0.1 at % oxygen, less than about 0.01 at % oxygen, or less than about 0.001 at % oxygen. In some embodiments a second reactant does not comprise O₂, H₂O or O₃.

Thus, in some embodiments the second reactant may comprise reactive species formed from compounds having both N and H, such as NH₃ and N₂H₄, a mixture of N₂/H₂ or other precursors having an N—H bond. In some embodiments the second reactant may be formed, at least in part, from N₂. In some embodiments the second reactant may be formed, at least in part, from H₂ and N₂, where the H₂ and N₂ are provided at a flow ratio (H₂/N₂), from about 100:1 to about 1:100, from about 20:1 to about 1:20, from about 10:1 to about 1:10, from about 5:1 to about 1:5 and/or from about 2:1 to about 4:1, and in some cases 1:1. For example, a hydrogen-containing plasma for depositing SiOCN can be generated using both N₂ and H₂ at one or more ratios described herein.

In some embodiments, a hydrogen plasma may be free or substantially free of nitrogen-containing species (e.g., nitrogen ions, radicals, atomic nitrogen). For example, nitrogen-containing gas is not used to generate the hydrogen plasma. In some embodiments, nitrogen-containing gas (e.g., N₂ gas) is not flowed into the reaction chamber during the hydrogen plasma step.

In some embodiments the second reactant may comprise reactive species formed from compounds containing N. In some embodiments the second reactant may be formed from N₂. That is, in some embodiments the reactive species are generated from a gas containing nitrogen, such as N₂. In some embodiments the second reactant may comprise reactive species generated from N₂. In some embodiments the second reactant is reactive species generated from N₂.

In some embodiments the second reactant may comprise reactive species formed by a plasma from an inert gas such as a noble gas, for example Ar or He. In some embodiments the second reactant may comprise reactive species formed by a plasma from one or more gases, for example a nitrogen-containing gas and a noble gas such as Ar or He. In some embodiments the second reactant does not comprise hydrogen. In some embodiments the second reactant does not comprise reactive species formed from compounds containing H.

In some embodiments, a hydrogen plasma may be free or substantially free of oxygen-containing species (e.g., oxygen ions, radicals, atomic oxygen). For example, oxygen-containing gas is not used to generate the hydrogen plasma. In some embodiments, oxygen-containing gas (e.g., O₂ gas) is not flowed into the reaction chamber during the hydrogen plasma step.

In some embodiments, the second reactant does not comprise any species generated from nitrogen. Thus, in some embodiments reactive species are not generated from a gas containing nitrogen. In some embodiments a second reactant comprising reactive species is generated from a gas that does not contain nitrogen. For example in some embodiments a second reactant may comprise a plasma generated from a gas that does not contain nitrogen. In some embodiments the second reactant may be generated from a gas containing less than about 1 atomic % (at %) nitrogen, less than about 0.1 at % nitrogen, less than about 0.01 at % nitrogen, or less than about 0.001 at % nitrogen. In some embodiments a second reactant does not comprise N₂, NH₃ or N₂H₄.

In some embodiments oxygen-containing gas is not used to generate the hydrogen plasma. In some embodiments, oxygen-containing gas (e.g., O₂ gas) is not flowed into the reaction chamber during the hydrogen plasma step.

In some embodiments the gas used to generated reactive species, such as plasma, may consist essentially of hydrogen. In some embodiments the gas used to generated reactive species, such as plasma, may consist essentially of nitrogen. In some embodiments the gas used to generated reactive species, such as plasma, may consist essentially of argon or another noble gas. In some embodiments, a plasma power used for generating a hydrogen-containing plasma can be about 10 Watts (W) to about 2,000 W, about 50 W to about −1000 W, about 100 W to about 1000 W or about 100 W to about 500 W. In some embodiments, a plasma power used for generating a hydrogen-containing plasma can be about 100 W to about 300 W. In some embodiments the plasma power may be gradually or incrementally increased or decreased over a number of deposition cycles. For example in some embodiments a plasma power used for generating a hydrogen-containing plasma can be about 100 W for a first number of deposition cycles, and may be increased to 200 W for a second number of deposition cycles, and may further be increased to 400 W for a third number of deposition cycles.

SiOCN Film Characteristics

SiOCN thin films deposited according to some of the embodiments discussed herein may achieve impurity levels or concentrations below about 3 at %, below about 1 at %, below about 0.5 at %, or below about 0.1 at %. In some thin films, the total impurity level excluding hydrogen may be below about 5 at %, below about 2 at %, below about 1 at %, or below about 0.2 at %. And in some thin films, hydrogen levels may be below about 30 at %, below about 20 at %, below about 15 at %, or below about 10 at %. As used herein, an impurity may be considered any element other than Si, O, C, and/or N.

In some embodiments, the deposited SiOCN films do not comprise an appreciable amount of hydrogen. However, in some embodiments a SiOCN film comprising hydrogen is deposited. In some embodiments, the deposited SiOCN films comprises less than about 30 at %, less than about 20 at %, less than about 15 at %, less than about 10 at % or less than about 5 at % of hydrogen. In some embodiments the thin films do not comprise argon.

According to some embodiments, the SiOCN thin films may exhibit step coverage and pattern loading effects of greater than about 50%, greater than about 80%, greater than about 90%, or greater than about 95%. In some cases step coverage and pattern loading effects can be greater than about 98% and in some case about 100% (within the accuracy of the measurement tool or method). In some embodiments step coverage and pattern loading effects can be greater than about 100%, greater than about 110%, greater than about 120%, greater than about 130%, or greater than about 140%. These values can be achieved in features with aspect ratios of 2 or greater, in some embodiments in aspect ratios of about 3 or greater, in some embodiments in aspect ratios of about 5 or greater and in some embodiments in aspect ratios of about 8 or greater.

In some embodiments the step coverage may be between about 50% and about 110%, between about between about 80% and about 110%, between about 90% and about 110%, between about 95% and 110%, between about 98% and 110%, or between about 100% and 110%. In some embodiments the step coverage may be between about 50% and about 100%, between about between about 80% and about 100%, between about 90% and about 100%, between about 95% and 100%, or between about 98% and 100%.

In some embodiments the growth rate of the film is from about 0.01 Å/cycle to about 5 Å/cycle, from about 0.05 Å/cycle to about 2 Å/cycle. In some embodiments the growth rate of the film is more than about 0.05 Å/cycle, more than about 0.1 Å/cycle, more than about 0.15 Å/cycle, more than about 0.3 Å/cycle, more than about 0.3 Å/cycle, more than about 0.4 Å/cycle. As used herein, “pattern loading effect” is used in accordance with its ordinary meaning in this field. While pattern loading effects may be seen with respect to impurity content, density, electrical properties and etch rate, unless indicated otherwise the term pattern loading effect when used herein refers to the variation in film thickness in an area of the substrate where structures are present. Thus, the pattern loading effect can be given as the film thickness in the sidewall or bottom of a feature inside a three-dimensional structure relative to the film thickness on the sidewall or bottom of the three-dimensional structure/feature facing the open field. As used herein, a 100% pattern loading effect (or a ratio of 1) would represent about a completely uniform film property throughout the substrate regardless of features i.e. in other words there is no pattern loading effect (variance in a particular film property, such as thickness, in features vs. open field).

In some embodiments, SiOCN films are deposited to a thickness of from about 3 nm to about 50 nm, from about 5 nm to about 30 nm, from about 5 nm to about 20 nm. These thicknesses can be achieved in feature sizes (width) below about 100 nm, about 50 nm, below about 30 nm, below about 20 nm, and in some cases below about 15 nm. According to some embodiments, a SiOCN film is deposited on a three-dimensional structure and the thickness at a sidewall may be slightly even more than 10 nm. In some embodiments SiOCN films of greater than 50 nm can be deposited. In some embodiments SiOCN films of greater than 100 nm can be deposited. In some embodiments, SiOCN films are deposited to a thickness of more than about 1 nm, more than about 2 nm, more than about 3 nm, more than about 5 nm, more than about 10 nm. According to some embodiments SiOCN films with various wet etch rates (WER) may be deposited. When using a blanket WER in 0.5 wt % dHF (nm/min), SiOCN films may have WER values of less than about 5, less than about 4, less than about 2, or less than about 1. In some embodiments SiOCN films may have WER values significantly less than 1. In some embodiments SiOCN films may have WER values less than about 0.3, less than about 0.2, or less than about 0.1. In some embodiments SiOCN films may have WER values less than about 0.05, less than about 0.025, or less than about 0.02.

The blanket WER in 0.5 wt % dHF (nm/min) relative to the WER of thermal oxide may be less than about 3, less than about 2, less than about 1, and less than about 0.5. In some embodiments the blanket WER in 0.5 wt % dHF relative to the WER of TOX may be less than about 0.1.

In some embodiments wherein a PEALD process is carried out at temperatures less than about 100° C., The blanket WER in 0.5 wt % dHF (nm/min) relative to the WER of thermal oxide may be less than about 10, less than about 5, less than about 3, and less than about 2, or less than about 1.

And in some embodiments, a ratio of a sidewall etch rate, for example a WER of a SiOCN film deposited on a substantially vertical three dimensional feature, such as a fin or trench relative to the etch rate of the SiOCN film deposited on a substantially horizontal surface, such as the top surface of a three dimensional feature, such as fin or trench, in 0.5 wt % dHF may be from about 1 to about 2, from about 2 to about 5, from about 5 to about 10, from about 10 to about 20, or in some cases greater than or equal to about 20. In some embodiments a ratio of the WER of a SiOCN film deposited on a three dimensional feature to the WER of a SiOCN film deposited on the top surface of a three dimensional feature may be equal to or greater than about 2, equal to or greater than about 5, equal to or greater than about 10, equal to or greater than about 15, or equal to or greater than about 20.

In some embodiments a ratio of the WER of a SiOCN film deposited on or in a substantially vertical surface of a three dimensional feature, for example a sidewall surface, to the WER of a SiOCN film deposited on or in a substantially horizontal surface of a three dimensional feature, for example a top surface, may be from about 1 to about 0.5, from about 0.5 to about 0.2, from about 0.2 to about 0.1, from about 0.1 to about 0.05, or in some cases less than about 0.05. In some embodiments a ratio of the WER of a SiOCN film deposited on a substantially vertical surface of a three dimensional feature to the WER of a SiOCN film deposited on a substantially horizontal surface of a three dimensional feature may be equal to or less than about 0.5, equal to or less than about 0.2, equal to or less than about 0.1, or equal to or less than about 0.05.

In some embodiments a ratio of the WER of a SiOCN deposited according to processes described herein to a WER of TOX may be between about 5 to about 10, between about 2 to about 5, between about 1 to about 2, between about 0.5 to about 1, or between about 0.1 to about 0.5. In some embodiments a ratio of the WER of a SiOCN deposited according to processes described herein to a WER of TOX may be greater than or equal to about 0.1, greater than or equal to about 0.5, greater than or equal to about 1, greater than or equal to about 2, greater than or equal to about 5, or greater than or equal to about 10.

In some embodiments, SiOCN formed according to one or more processes described herein can advantageously demonstrate a ratio of a WER of a substantially vertical region to a WER of a substantially horizontal region of about 1, for example in 0.5 wt % dHF. For example, a ratio of a wet etch rate of a SiOCN thin film formed over substantially vertical surfaces (e.g., sidewall surfaces) to a wet etch rate of the SiOCN thin film formed over substantially horizontal surfaces (e.g., top surfaces) of three-dimensional structures on a substrate surface can be the same or substantially the same. In some embodiments, the ratio can be about 4 to about 0.5, about 2 to about 0.75, about 1.25 to about 0.8, or about 1.1 to about 0.9. These ratios can be achieved in features with aspect ratios of about 2 or more, about 3 or more, about 5 or more or even about 8 or more.

In some embodiments, the amount of etching of SiOCN films according to the present disclosure may be about 1, 2, 5, 10 or more times less than an amount of etching observed for thermal SiO₂ (TOX) in a 0.5% HF-dip process (for example in a process in which about 2 to about 3 nm TOX is removed, 1, 2, 5, 10 or more times less SiOCN is removed when deposited according to the methods disclosed herein).

In some embodiments less than about 2 nm of SiOCN film may be removed in a 0.5% HF-dip process with an etching time of 5 minutes. In some embodiments less than about 2 nm of SiOCN film may be removed in a 0.5% HF-dip process with an etching time of 60 minutes.

All atomic percentage (i.e., at %) values provided herein exclude hydrogen for simplicity and because hydrogen is difficult to accurately analyze quantitatively, unless otherwise indicated. However, in some embodiments, if it is possible to analyze the hydrogen with reasonable accuracy, the hydrogen content of the films is less than about 20 at %, less than about 10 at % or less than about 5 at %. In some embodiments the deposited SiOCN thin film may contain up to about 70% oxygen on an atomic basis (at %). In some embodiments a SiOCN film may comprise oxygen from about 10% to about 70%, from about 15% to about 50%, or from about 20% to about 40% on an atomic basis. In some embodiments a SiOCN film may comprise at least about 20%, about 40% or about 50% oxygen on an atomic basis.

In some embodiments the deposited SiOCN thin film may contain up to about 40% carbon on an atomic basis (at %). In some embodiments a SiOCN film may comprise carbon from about 0.5% to about 40%, from about 1% to about 30%, or from about 5% to about 20% on an atomic basis. In some embodiments a SiOCN film may comprise at least about 1%, about 10% or about 20% carbon on an atomic basis.

In some embodiments the deposited SiOCN thin film may contain up to about 30% nitrogen on an atomic basis (at %). In some embodiments a SiOCN film may comprise nitrogen from about 0.51% to about 30%, from about 1% to about 20%, or from about 3% to about 15% on an atomic basis. In some embodiments an SiOCN film may comprise at least about 1%, about 5% or about 10% nitrogen on an atomic basis.

In some embodiments the deposited SiOCN thin film may contain up to about 50% silicon on an atomic basis (at %). In some embodiments a SiOCN film may comprise silicon from about 10% to about 50%, from about 15% to about 40%, or from about 20% to about 35% on an atomic basis. In some embodiments a SiOCN film may comprise at least about 15%, about 20%, about 25% or about 30% silicon on an atomic basis.

In some embodiments the deposited SiOCN thin film may comprise from about 30 at % to about 40 at % silicon, from about 25 at % to about 40 at % oxygen, from about 10 at % to about 20 at % C, and about 10 at % nitrogen. In some embodiments the deposited SiOCN film may comprise about 33% silicon and about 67% oxygen. As discussed above, in some embodiments a SiOCN film may comprise Si—C bonds, Si—O bonds, and/or Si—N bonds. In some embodiments a SiOCN film may comprise Si—C bonds and Si—O bonds and may not comprise Si—N bonds. In some embodiments a SiOCN film may comprise Si—N bonds and Si—O bonds and may not comprise Si—C bonds. In some embodiments a SiOCN film may comprise Si—N bonds and Si—C bonds and may not comprise Si—O bonds. In some embodiments the SiOCN films may comprise more Si—O bonds than Si—C bonds, for example a ratio of Si—O bonds to Si—C bonds may be from about 1:1 to about 10:1. In some embodiments a deposited SiOCN film may comprise one or more of SiN, SiO, SiC, SiCN, SiON, and/or SiOC.

In some embodiments a SiOCN film is not a low-k film, for example a SiOCN film is not a porous film. In some embodiments a SiOCN is a continuous film. In some embodiments a SiOCN film has a k-value that is less than about 10. In some embodiments a SiOCN film has a k-value that is less than about 7. In some embodiments a SiOCN film has a k-values from about 3.9 to about 10. In some embodiments a SiOCN film has a k-value that is less than about 5.5, less than about 5.0, less than about 4.8, less than about 4.6. In some embodiments a SiOCN film has a k-value that from about 3.8 to about 7, from about 3.8 to about 5.5, from about 3.8 to about 5.0, from about 4.0 to about 4.8, from about 4.1 to about 4.7. In some embodiments a SiOCN film has a k-value that is more than k-value of any low-k film. In some embodiments a SiOCN film has a k-value that is more than pure SiO₂.

In some embodiments SiOCN films deposited according to the present disclosure do not comprise a laminate or nanolaminate structure.

In some embodiments a SiOCN film deposited according to the present disclosure is not a self-assembled monolayer (SAM). In some embodiments a SiOCN film deposited according to the present disclosure does not consist of separate, individual molecules which are not bonded to each other. In some embodiments a SiOCN film deposited according to the present disclosure comprises a material which is substantially bonded or linked together. In some embodiments a SiOCN film deposited according to the present disclosure is not a functional layer, is not amino-functionalized, and/or is not used as a functional surface. In some embodiments a SiOCN film deposited according to the present disclosure is not terminated with —NH₂ groups. In some embodiments a SiOCN film deposited according to the present disclosure does not contain a substantial amount of —NH₂ groups.

Integration

In some embodiments a SiOCN thin film deposition process as described herein may be used to form SiOCN thin films for use in, for example, in a multiple patterning process such as a self-aligned patterning process. In some embodiments an SiOCN thin film may be formed or deposited on a substrate comprising an organic material, for example a patterned organic material comprising a photoresist, as part of a multiple patterning process. In some embodiments a SiOCN deposition process as described herein may be used as part of a spacer-defined double patterning (SDDP) process or a spacer-defined quadruple patterning (SDQP) process.

By way of example, in a direct SDDP process SiOCN is conformally deposited via a plasma enhanced ALD process as described herein and according to some embodiments in a reaction space on a substrate comprising a patterned resist layer, such as a patterned photoresist layer comprising a three-dimensional resist feature. The SiOCN film deposited by a PEALD process as described herein has a smooth boundary with the resist feature and does not significantly damage, degrade, or deform the resist feature. The conformal and smooth SiOCN film can then be directionally etched so that SiOCN is removed from the horizontal surfaces of the resist feature and substrate, leaving only the SiOCN deposited on or extending from the sidewalls of the resist feature. The resist can then be removed via an etching process, leaving behind the SiOCN spacers.

In some embodiments the substrate comprises a thermal SiO₂ layer on a silicon substrate. In some embodiments the substrate comprises a silicon based layer, such as a Si, SiO₂ or SiN_(x) layer on a silicon substrate. In some embodiments the substrate comprises a sacrificial layer. In some embodiments the substrate comprises a polymer or resist material such as a photoresist material. In some embodiments the substrate comprises at least one feature, such as a three-dimensional raised feature. In embodiments the feature comprises an elevated structure that includes substantially vertical sidewalls. In some embodiments of the invention the feature is comprises a feature of a patterned photoresist film.

By way of further example, in a direct SDQP process a first SiOCN film is conformally deposited in a reaction space on a substrate comprising a patterned resist layer, such as a patterned photoresist layer comprising a three-dimensional resist feature, via a PEALD process according to some embodiments including a second reactant comprising reactive species generated from N₂. However, in some embodiments a SiOCN film may be deposited by a process including a first number of deposition cycles including a second reactant comprising reactive species generated by a plasma from a nitrogen-containing gas and/or an inert gas such as a noble gas, and a second number of deposition cycles including hydrogen plasma as a second reactant. For example, a SiOCN film may be deposited by a process including a first number of deposition cycles including nitrogen plasma as a second reactant and a second number of deposition cycles including hydrogen plasma as a second reactant.

The first SiOCN film deposited by a PEALD process as described herein has a smooth boundary with the resist feature and does not significantly damage, degrade, or deform the resist feature. The conformal and smooth first SiOCN film can then be directionally etched so that SiOCN is removed from the horizontal surfaces of the resist feature and substrate, leaving only the SiOCN deposited on or extending from the sidewalls of the resist feature. The resist can then be removed via an etching process, leaving behind a first SiOCN feature.

This first SiOCN feature can be subjected to a chemical mechanical polish (CMP) to provide a substantially flat top surface. A second SiOCN film is conformally deposited in a reaction space on the substrate comprising the first SiOCN feature via a PEALD process according to some embodiments including a second reactant comprising reactive species generated from H₂. The conformal and smooth second SiOCN film can then be directionally etched so that SiOCN is removed from the horizontal surfaces of the first SiOCN feature and substrate, leaving only the SiOCN deposited on or extending from the sidewalls of the first SiOCN feature. The first SiOCN film can then be removed, leaving behind the SiOCN spacers.

As shown in FIG. 6, a SiOCN film 601 conformally deposited via a plasma enhanced ALD process as described herein and according to some embodiments in a reaction space on a substrate comprising a patterned organic layer, such as a patterned photoresist layer comprising a three-dimensional resist feature may not significantly damage, degrade, or deform the resist feature as compared to a SiOCN film 602 deposited by a substantially similar PEALD process including an oxygen-containing plasma. In some embodiments a SiOCN film may be deposited on an organic material, such as a three-dimensional resist feature without substantially deforming the structure or shape of the three-dimensional resist feature. For example, a SiOCN film may be deposited according to some embodiments and may not cause significant rounding of the edges of a three-dimensional resist feature on which it is deposited.

Example 1

Exemplary SiOCN thin films were deposited by a PEALD process as described herein. The deposition temperature was 300° C. and APTMS was used as a silicon precursor. A plasma was generated by applying 200 W of RF power to the second reactant. A mixture of H₂ and N₂ was used as the second reactant, which was supplied with an Ar carrier gas. FIG. 2 illustrates the growth per cycle (Å/cycle), refractive index, and WERR as compared with TOX as a function of second reactant gas ratio for SiOCN films deposited by a PEALD process as described herein. The second reactant gas ratio is shown along the X-axis of FIG. 2, and represents the ratio of N₂ to both H₂ and N₂ (N₂:(H₂+N₂)) in the second reactant.

As can be seen in FIG. 2, the growth rate of the SiOCN films increased as the N₂:(H₂+N₂) ratio in the second reactant increased. The refractive index of the deposited films decreased as the N₂:(H₂+N₂) ratio in the second reactant increased. The ratio of the WER of the deposited SiOCN films to the WER of TOX (WERR to TOX) was observed to increase as the N₂:(H₂+N₂) ratio in the second reactant increased. Significantly, the WERR to TOX was for SiOCN films deposited with N₂:(H₂+N₂) ratios of 50% and 0% (no N₂ present in the second reactant) was observed to be less than 1. Without being bound by any one theory, it is believed that the presence of H2 in the second reactant results in high wet chemical resistance in the deposited SiOCN thin film.

FIG. 3 illustrates the etching amount versus etching time for both SiOCN thin films deposited by PEALD processes as described herein and TOX. The etching process was a 0.5% HF-dip process. As can be seen in FIG. 3, the deposited SiOCN exhibits significantly greater etch resistance than TOX. After exposure to a 60 minute dip in 0.5% HF less than 2 nm of SiOCN film was removed.

The composition of a SiOCN film deposited by a PEALD process as described herein was analysed using X-ray photoelectron spectroscopy (XPS). The deposition temperature was 300° C. and APTMS was used as a silicon precursor. The results are shown in Table 1, below. Two distinct Si bonding energies were identified, indicating the presence of Si—C and SiO bonds in the deposited film.

TABLE 1 Film composition measure by XPS Depth (Å) O N C Si_(SiC) Si_(SiOCN) 0 46.3 5.3 18.6 5.3 24.5 25 41.4 9.0 11.5 6.7 31.5 50 41.5 8.8 11.0 7.0 31.7 75 41.0 8.9 11.0 5.3 33.8 100 41.9 8.9 10.7 6.3 32.3 125 42.0 9.3 10.0 5.9 32.8 150 43.0 8.1 10.7 5.7 32.5 175 43.9 8.3 9.7 4.7 33.4 200 44.5 8.2 9.0 5.9 32.4 225 45.0 8.3 9.1 5.2 32.4 250 46.0 7.9 8.4 4.1 33.6 275 47.3 7.5 8.3 5.0 31.8 300 47.8 7.4 7.5 4.6 32.8

FIG. 4 also illustrates film composition as a function depth for an exemplary SiOCN film deposited by a PEALD process as described herein.

Example 2

FIGS. 5A and 5B are scanning electron microscopy (SEM) images showing cross-section view of SiOCN films formed on trench structure prior to and after exposure to a 2 minutes dip in dHF wet etch solution, respectively. The SiOCN films of FIGS. 5A and 5B were formed according to the PEALD processes as described herein. The deposition temperature was 300° C. and APTMS was used as a silicon precursor. A plasma was generated by applying 400 W of RF power to the second reactant comprising H₂. The plasma pulse time was 8 seconds. FIGS. 5C and 5D are scanning electron microscopy (SEM) images showing cross-section view of SiOCN films formed on trench structure prior to and after exposure to a 2 minutes dip in dHF wet etch solution, respectively. The SiOCN films of FIGS. 5C and 5D were formed according to the PEALD processes as described herein. The deposition temperature was 300° C. and APTMS was used as a silicon precursor. A plasma was generated by applying 400 W of RF power to the second reactant comprising H₂ and N₂. The plasma pulse time was 8 seconds.

As shown in FIGS. 5A and 5C, the SiOCN film formed using a PEALD process with a second reactant that did not comprise N₂ demonstrated improved conformaltity prior to the wet etch dip, as compared to the SiOCN film formed using a PEALD process with a second reactant comprising H₂ and N₂. The SiOCN film formed with a second reactant that did not comprise N₂ had a step coverage of 114% to 136%, while the SiOCN film formed with a second reactant comprising H₂ and N₂ had a step coverage of 54%. As shown in FIGS. 5B and 5D, the conformality of the SiOCN film formed using a second reactant that did not comprise N₂ was maintained subsequent to the wet etch dip, while that of the SiOCN film formed using a second reactant comprising H₂ and N₂ was decreased.

Additionally, the SiOCN film formed using a second reactant that did not comprise N₂ demonstrated a wet etch rate ratio to TOX (WERR to TOX) of 0.2 for the horizontal regions of the film and a WERR to TOX of 1.0 for the vertical regions of the film (sidewall surfaces). The SiOCN film formed using a second reactant comprising H₂ and N₂ demonstrated a wet etch rate ratio to TOX (WERR to TOX) of 2.0 for the horizontal regions of the film deposited on top of the trench structure, a WERR to TOX of 1.4 for the regions of the film deposited on the bottom of the trench structure, and a WERR to TOX of 1.6 for the vertical regions of the film (sidewall surfaces).

Example 3

Exemplary SiOCN films were deposited according to the methods described herein. SiOCN films were deposited by a PEALD process according to some embodiments including a plurality of deposition cycles including APTMS as a silicon precursor and a second reactant comprising reactive species generated by a plasma from N₂ and a hydrogen plasma cycle repeated after a given number of deposition cycles. The hydrogen plasma cycle included contacting the substrate with a reactive species generated by a plasma from H₂ for about 4 seconds.

Sample SiOCN films were prepared by the above-described methods including repeating a hydrogen plasma cycle after every 3 deposition cycles, after every 5 deposition cycles, and after every 10 deposition cycles. It was found that the inclusion of a hydrogen plasma cycle reduced overall film thickness by about 20% to 40% as compared to a film deposited by a method that did include a hydrogen plasma cycle. The refractive index of the sample SiOCN films was measured and was found to be about 0.1 to 0.2 lower as compared to a film deposited via a method that did include a hydrogen plasma cycle. It was also found that the growth per cycle (GPC) increased approximately linearly with increasing number of deposition cycles between hydrogen plasma cycles.

The sample SiOCN films were also found to be thicker than a sample SiOCN film deposited according to a similar deposition method but including a second reactant comprising reactive species generated by a plasma from H₂ and not including a hydrogen plasma cycle.

Another sample SiOCN film was prepared as described above, however the hydrogen plasma cycle had a contacting time of 20 seconds. This sample was found to have a lower refractive index, about 1.45, than the sample films prepared according to a method including a hydrogen plasma contacting time of 4 seconds.

Example 4

Sample SiOCN films were deposited on a substrate having a surface comprising a polyimide film. The sample SiOCN films were deposited by a PEALD method as described herein including a first nitrogen-containing plasma deposition step and a second hydrogen-containing plasma deposition step. The first nitrogen-containing plasma deposition step used APTMS as a silicon precursor and a second reactant comprising reactive species generated by a plasma from N₂ to form a first SiOCN layer. The second hydrogen-containing plasma deposition step included APTMS as a silicon precursor and a second reactant comprising reactive species generated by a plasma from H₂ to form a second SiOCN layer.

The final thickness of the sample SiOCN film was compared with a calculated thickness based on the cumulative thicknesses of separate sample depositions of the first and second SiOCN layers directly on thermal silicon oxide. The measured thickness of the sample SiOCN film was found to approach the calculated thickness as the number of first nitrogen-containing plasma deposition step cycles increased. A SiOCN sample film deposited with 100 first nitrogen-containing plasma deposition step cycles was found to be about 80% of the calculated film thickness, while a SiOCN sample film deposited with 300 first nitrogen-containing plasma deposition step cycles was found to be about the calculated film thickness. A large mismatch between calculated film thickness and sample film thickness was observed for sample SiOCN films deposited with 50 or fewer first nitrogen-containing plasma deposition step cycles, the sample film having a thickness of about 25% of the calculated film thickness.

Without being bound by any one theory, it is believed that a nitrogen-containing plasma deposition step having 50 or fewer cycles resulted in a first SiOCN layer that was too thin to effectively protect the organic substrate surface from degradation due to the second hydrogen-containing plasma deposition step, with the loss of organic surface material causing the reduced measured film thickness.

Another sample SiOCN film was prepared by a method including a first nitrogen-containing plasma deposition step having 50 cycles and a second hydrogen-containing plasma deposition step having 100 cycles with a plasma power of 100 W followed by 100 cycles with a plasma power of 200 W and 300 cycles with a plasma power of 400 W. It was found that by gradually increasing the plasma power of the second hydrogen-containing plasma deposition step, the organic substrate surface was sufficiently protected from degradation due to the second hydrogen-containing plasma deposition step, even with a relatively thin first SiOCN layer.

Example 5

FIG. 7 shows a sample SiOCN film 701 deposited on a substrate comprising a three-dimensional trench structure by a PEALD process as described herein utilizing APTMS as a silicon precursor and a second reactant comprising reactive species generated by a plasma from H₂ flowed into the reaction chamber at 100 sccm. The pressure in the reaction chamber during deposition was 4 Torr, the temperature was 225° C., and the second reactant was generated by applying 200 W of RF power to the second reactant. The silicon precursor was pulsed into the reaction chamber for 4 seconds and purged for 4 seconds in each deposition cycle, while the second reactant was pulsed into the reaction chamber for 4 seconds and purged for 0.5 seconds.

The sample SiOCN film was then exposed to 0.5 wt % dHF for 2 minutes. The etched sample SiOCN film 702 showed a ratio of the wet etch rate of the SiOCN film deposited on the vertical surfaces of the substrate to the wet etch rate of the SiOCN film deposited on the horizontal surfaces of the substrate of about 21.

As used herein, the term “about” may refer to a value that is within 15%, within 10%, within 5%, or within 1% of a given value.

The terms “film” and “thin film” are used herein for simplicity. “Film” and “thin film” are meant to mean any continuous or non-continuous structures and material deposited by the methods disclosed herein. For example, “film” and “thin film” could include 2D materials, nanorods, nanotubes or nanoparticles or even single partial or full molecular layers or partial or full atomic layers or clusters of atoms and/or molecules. “Film” and “thin film” may comprise material or layer with pinholes, but still be at least partially continuous.

It will be understood by those of skill in the art that numerous and various modifications can be made without departing from the spirit of the present invention. The described features, structures, characteristics and precursors can be combined in any suitable manner. Therefore, it should be clearly understood that the forms of the present invention are illustrative only and are not intended to limit the scope of the present invention. All modifications and changes are intended to fall within the scope of the invention, as defined by the appended claims. 

What is claimed is:
 1. A method of forming a silicon oxycarbonitride (SiOCN) thin film on a substrate in a reaction space by a plasma enhanced atomic layer deposition (PEALD) process, wherein the PEALD process comprises at least one deposition cycle comprising: contacting a surface of the substrate with a vapor phase silicon precursor to thereby adsorb a silicon species on the surface of the substrate; contacting the adsorbed silicon species with at least one reactive species generated by plasma formed from gas that does not comprise oxygen; optionally repeating the contacting steps until a SiOCN film of a desired thickness has been formed; and a hydrogen plasma treatment cycle carried out after a predetermined number of deposition cycles, the hydrogen plasma treatment cycle comprising contacting the substrate with a reactive species generated by a plasma from hydrogen; wherein the silicon precursor is selected from the group consisting of the following general formulas: (R^(I)O)_(4-x)Si(R^(II)—NH₂)_(x)  (1) wherein x is an integer from 1 to 4; R^(I) is independently selected from the group consisting of alkyl groups; and R^(II) is independently selected from the group consisting of hydrocarbon groups; (R^(I)O)₃Si—R^(II)—NH₂  (2) wherein R^(I) is independently selected from the group consisting of alkyl groups; and R^(II) is independently selected from the group consisting of hydrocarbon groups; (R^(I)O)_(4-x)Si(—[CH₂]_(n)—NH₂)_(x)  (3) wherein x is an integer from 1 to 4; n is an integer from 1-5; and R^(I) is independently selected from the group consisting of alkyl groups.
 2. The method of claim 1, wherein the SiOCN thin film is deposited on a three-dimensional structure on the substrate.
 3. The method of claim 2, wherein a wet etch rate ratio of a wet etch rate of SiOCN formed on a substantially vertical surface of the three-dimensional structure to a wet etch rate of the SiOCN formed on a substantially horizontal surface of the three-dimensional structure is more than about 5:1 in 0.5 wt % dilute HF.
 4. The method of claim 2, wherein a wet etch rate ratio of a wet etch rate of SiOCN formed on a substantially vertical surface of the three-dimensional structure to a wet etch rate of the SiOCN formed on a substantially horizontal surface of the three-dimensional structure is less than about 1:2 in 0.5 wt % dilute HF.
 5. The method of claim 1, wherein the silicon precursor comprises (3-aminopropyl)trimethoxysilane (APTMS).
 6. The method of claim 1, wherein the reactive species comprises hydrogen plasma, hydrogen atoms, hydrogen radicals, or hydrogen ions.
 7. The method of claim 1, wherein the reactive species is generated from a second reactant comprising a noble gas.
 8. The method of claim 6, wherein the reactive species further comprises nitrogen plasma, nitrogen atoms, nitrogen radicals, or nitrogen ions.
 9. The method of claim 6, wherein the second reactant comprises H₂.
 10. The method of claim 1, wherein the substrate surface comprises an organic material.
 11. The method of claim 10, wherein the organic material comprises a photoresist material.
 12. The method of claim 1, wherein a ratio of one or more hydrogen plasma treatment cycles carried out at one or more intervals after a predetermined number of deposition cycles to deposition cycles is from about 1:1 to about 1:10.
 13. The method of claim 1, wherein the at least one reactive species generated by plasma formed from a gas that does not comprise oxygen comprises reactive species generated by a plasma from N₂.
 14. The method of claim 13, further comprising a second hydrogen plasma deposition step performed after a predetermined number of deposition cycles have been carried out, the hydrogen plasma deposition step comprising at least one cycle comprising: contacting a surface of the substrate with a vapor phase silicon precursor to on the surface of the substrate; contacting the adsorbed silicon species with a reactive species generated by plasma formed from H₂; and optionally repeating the contacting steps until a SiOCN film of a desired thickness has been formed; wherein the silicon precursor has a formula as in one of the following general formulas: (R^(I)O)_(4-x)Si(R^(II)—NH₂)_(x)  (1) wherein x is an integer from 1 to 4; R^(I) is independently selected from the group consisting of alkyl groups; and R^(II) is independently selected from the groups consisting of hydrocarbon groups; (R^(I)O)₃Si—R^(II)—NH₂  (2) wherein R^(I) is independently selected from the group consisting of alkyl groups; and R^(II) is independently selected from the group consisting of hydrocarbon groups; (R^(I)O)_(4-x)Si(—[CH₂]_(n)—NH₂)_(x)  (3) wherein x is an integer from 1 to 4; n is an integer from 1-5; and R^(I) is independently selected from the group consisting of alkyl groups.
 15. The method of claim 14, wherein the method is used to form SiOCN spacers on a substrate in a spacer defined double patterning (SDDP) process.
 16. The method of claim 14, wherein the method is used to form SiOCN spacers on a substrate in a spacer defined quadruple patterning (SQDP) process.
 17. The method of claim 1, wherein a reactive species is generated by applying RF power of 100 Watts (W) to about 1000 W to the second reactant.
 18. The method of claim 1, wherein the deposition cycle is carried out at a process temperature of about 300° C. to about 400° C.
 19. The method of claim 1, wherein the deposition cycle is carried out at a process temperature of less than about 100° C. 